Intermediate infrared gallate glass as well as preparation method and application thereof

Abstract

The invention provides mid-infrared gallate glass as well as a preparation method and application thereof, and the mid-infrared gallate glass comprises the following components in percentage by mass of oxides: 26-35% of Ga2O3, 10-20% of Ga2O3, 10-20% of Na2O, 10-20% of Na2O, 10-20% of Na2O, 10-20% of 39%-47% of CaO; 3.1%-6.5% of Al2O3 (aluminum oxide); 0.5% to 13% of Y2O3; r: 11%-15%, wherein R is one or more of BaO, SrO and MgO; and M: 1%-5%, and M is Na2O and / or K2O. The mid-infrared gallate glass provided by the invention is high in permeability, good in mechanical property, high in stability and strong in adaptability to complex environments.

Description

Technical Field

[0001] The present invention relates to the technical field of optical glass materials, and in particular to mid-infrared gallate glass and a preparation method and application thereof. Background Art

[0002] Mid-wave infrared glass is a special glass material with infrared transmittance. It not only has excellent infrared transmittance, but also has the advantages of good optical uniformity, low manufacturing cost, and easy processing into large-size or complex-shaped products. It has always been the focus of infrared material research and application. Currently, the mid-infrared glass that has been put into practical use includes aluminate glass, gallate glass, heavy metal fluoride glass, etc.

[0003] With the rapid development of science and technology, the demand for optical imaging systems is increasing, especially for wide-band transparent window materials in the field of new-generation infrared optoelectronic systems. There is a large gap, and higher precision and wider detection range requirements are put forward for mid-infrared window materials, which requires window materials to have both high stability and a wider transmission band window. Among many mid-infrared glass systems, gallate glass has a wider infrared transmission range due to the weakly vibrating Ga-O bonds in gallate glass, and the infrared cutoff wavelength is red-shifted to 6.5μm to 7.0μm (aluminate glass cutoff wavelength is 5.7μm). For this reason, gallate glass has the potential to become a wide-band transparent window material for the new generation of infrared optoelectronic systems. However, the overall stability of the traditional gallate glass system is slightly poor. In actual application environments, its surface is prone to deliquesce and mold, which affects its transmission performance and performance as a window material.

[0004] In order to meet the demand for highly stable and wide-transmittance mid-infrared window materials in the field of new-generation infrared optoelectronic systems, it is of great significance to improve the stability of gallate glass. Summary of the invention

[0005] The main purpose of the present invention is to provide a mid-infrared gallate glass and a preparation method and application thereof. The technical problem to be solved is how to provide a mid-infrared gallate glass that has high transmittance, good mechanical properties, high stability, and strong adaptability to complex environments, so that it is more suitable for practical use.

[0006] The purpose of the present invention and the technical problem to be solved are achieved by adopting the following technical solutions. According to a mid-infrared gallate glass proposed by the present invention, its components, in terms of oxide mass percentage, include:

[0007] Ga2O3: 26%~35%;

[0008] CaO: 39%~47%;

[0009] Al2O3: 3.1%~6.5%;

[0010] Y2O3: 0.5%~13%;

[0011] R: 11% to 15%, wherein R is one or more of BaO, SrO, and MgO; and

[0012] M: 1% to 5%, M is Na2O and / or K2O.

[0013] The purpose of the present invention and the solution to its technical problems can be further achieved by adopting the following technical measures.

[0014] In some embodiments, in the aforementioned mid-infrared gallate glass,

[0015] Ga2O3: 29% to 31%; and / or,

[0016] CaO: 42% to 46%; and / or

[0017] Al2O3: 3.5% to 6.0%; and / or,

[0018] Y2O3:2%~10%.

[0019] In some embodiments, in the aforementioned mid-infrared gallate glass, BaO: 5% to 7%.

[0020] In some embodiments, in the aforementioned mid-infrared gallate glass, except for BaO, the sum of the contents of other alkaline earth metal oxides and M is 9% to 11%;

[0021] Among them, other alkaline earth metal oxides include SrO and / or MgO.

[0022] In some embodiments, the aforementioned mid-infrared gallate glass further comprises TeO2, and the content of TeO2 is ≤12%.

[0023] In some embodiments, the aforementioned mid-infrared gallate glass further comprises Sb2O3 as a component.

[0024] The purpose of the present invention and the technical problem solved by the present invention are also achieved by the following technical solutions. According to a method for preparing any of the aforementioned mid-infrared gallate glasses proposed by the present invention, the method comprises the following steps:

[0025] After mixing the ingredients according to the formula, glass raw materials are obtained, the aforementioned glass raw materials are mixed evenly, melted at 1450-1500° C. for 6-12 hours, and cooled to obtain primary melting clinker;

[0026] The aforementioned primary melting clinker is melted in a vacuum environment at a melting temperature of 1450-1550° C. for a melting time of 4-8 hours, and then formed, annealed and cooled to obtain a mid-infrared gallate glass.

[0027] The purpose of the present invention and the solution to its technical problems can be further achieved by adopting the following technical measures.

[0028] In some embodiments, in the aforementioned preparation method, the vacuum degree of the aforementioned vacuum environment is ≤3×10 -2 Pa.

[0029] The purpose of the present invention and the technical problem solved by the present invention are also achieved by the following technical solutions: A device proposed in the present invention comprises a window, wherein the window comprises any one of the aforementioned mid-infrared gallate glasses.

[0030] The purpose of the present invention and the solution to its technical problems can be further achieved by adopting the following technical measures.

[0031] In some embodiments, in the aforementioned device, the aforementioned device is an infrared detector, an infrared aircraft, a fairing or a hood.

[0032] Through the above technical solution, the mid-infrared gallate glass and its preparation method and application of the present invention have at least the following advantages:

[0033] The present invention provides a mid-infrared gallate glass and a preparation method and application thereof, wherein, in terms of oxide mass percentage, the components of the mid-infrared gallate glass include: Ga2O3: 26% to 35%; CaO: 39% to 47%; Al2O3: 3.1% to 6.5%; Y2O3: 0.5% to 13%; R: 11% to 15%, wherein R is one or more of BaO, SrO, and MgO; and M: 1% to 5%, wherein M is Na2O and / or K2O. The mid-infrared gallate glass provided by the present invention has high transmittance, good mechanical properties, high stability, and strong adaptability to complex environments.

[0034] The above description is only an overview of the technical solution of the present invention. In order to more clearly understand the technical means of the present invention and implement it according to the contents of the specification, the following is a detailed description of the preferred embodiments of the present invention in conjunction with the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 is a scanning calorimetry curve of the mid-infrared gallate glass in Example 1 of the present invention;

[0036] Figure 2 is the 0-8 μm infrared light transmittance curve of the mid-infrared gallate glass in Example 1 of the present invention;

[0037] Figure 3 is the infrared light transmittance curve of 700-1900nm of the mid-infrared gallate glass in Example 1 of the present invention;

[0038] Figure 4 is a scanning calorimetry curve of the mid-infrared gallate glass in Example 2 of the present invention;

[0039] Figure 5 is the infrared light transmittance curve of 0-8 μm of the mid-infrared gallate glass in Example 2 of the present invention;

[0040] Figure 6 This is the infrared light transmittance curve of the mid-infrared gallate glass in Example 2 of the present invention in the range of 700 to 1900 nm. DETAILED DESCRIPTION

[0041] In order to further explain the technical means and effects adopted by the present invention to achieve the predetermined invention purpose, the following is a detailed description of a mid-infrared gallate glass and its preparation method and its specific implementation, structure, features and effects proposed by the present invention in combination with the accompanying drawings and preferred embodiments. In the following description, different "one embodiment" or "embodiment" does not necessarily refer to the same embodiment. In addition, specific features, structures or characteristics in one or more embodiments may be combined in any suitable form.

[0042] It should be noted that, in the description of the present invention, unless otherwise specified, the meaning of "multiple" is greater than or equal to two; the terms "upper", "lower", "left", "right", "inner", "outer", etc., indicating the orientation or positional relationship, are only for the convenience of describing the present invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore cannot be understood as a limitation on the present invention. When the absolute position of the object being described changes, the relative positional relationship may also change accordingly.

[0043] In addition, the words "first", "second" and similar words used in the present invention do not indicate any order, quantity or importance, but are only used to distinguish different parts. "Vertical" is not strictly perpendicular, but is within the tolerance range. "Parallel" is not strictly parallel, but is within the tolerance range. "Include" or "comprising" and similar words mean that the elements before the word include the elements listed after the word, and do not exclude the possibility of including other elements.

[0044] It should also be noted that in the description of the present invention, unless otherwise clearly specified and limited, the terms "installed", "connected" and "connected" should be understood in a broad sense. For example, it can be a fixed connection, a detachable connection, or an integral connection; it can be directly connected or indirectly connected through an intermediate medium. For ordinary technicians in this field, the specific meanings of the above terms in the present invention can be understood according to the specific circumstances. When a specific device is described as being located between a first device and a second device, there may or may not be an intermediate device between the specific device and the first device or the second device.

[0045] The techniques, methods and equipment known to those of ordinary skill in the relevant art may not be discussed in detail, but where appropriate, the techniques, methods and equipment should be considered as part of the specification. The present invention provides these embodiments to make the present invention thorough and complete, and to fully express the scope of the present invention to those skilled in the art. It should be noted that unless otherwise specifically stated, the relative arrangement of the parts and steps, the composition of the materials, the numerical expressions and the numerical values ​​set forth in these embodiments should be interpreted as being merely exemplary, and not as limiting.

[0046] The present invention provides a mid-infrared gallate glass, which comprises, in terms of oxide mass percentage, the following components:

[0047] Ga2O3: 26%~35%;

[0048] CaO: 39%~47%;

[0049] Al2O3: 3.1%~6.5%;

[0050] Y2O3: 0.5%~13%;

[0051] R: 11% to 15%, wherein R is one or more of BaO, SrO, and MgO; and

[0052] M: 1% to 5%, M is Na2O and / or K2O.

[0053] Specifically, Ga2O3 is an important network former of mid-infrared gallate glass, which can improve the glass forming ability and chemical stability of the glass. The mass fraction of this component is controlled between 26% and 35%, preferably between 29% and 31%. If the mass fraction of this component is less than 26%, the glass forming ability of the glass will deteriorate; if the mass content of this component exceeds 35%, the elastic modulus and chemical stability of the glass will deteriorate.

[0054] CaO is a necessary component for mid-infrared gallate glass to have good elastic modulus and chemical stability. The mass fraction of this component is controlled between 39% and 47%, preferably between 42% and 46%, which can promote the compactness of the glass structure and improve the acid resistance stability of the glass. If the mass fraction of this component is less than 39%, the improvement of the elastic modulus and chemical stability of the glass is not obvious. If the mass fraction of this component exceeds 47%, the glass is difficult to fully melt and the glass forming properties are deteriorated.

[0055] Al2O3 can form a network structure with SiO2, making the glass structure compact and improving the mechanical properties and stability of the glass. The mass fraction of this component is controlled between 3.1% and 6.5%, preferably between 3.5% and 6%. If the Al2O3 content is lower than 3.1%, the internal network structure of the glass is small, and the strength, transmittance and other properties are low, and the network gap is small; if the content is higher than 6.5%, the melting temperature is too high, and defects such as stones will be caused.

[0056] Y2O3 is a network outer body of glass, which is used to reduce the melting temperature of glass and facilitate the discharge of bubbles during the melting process. The mass fraction of this component is controlled between 0.5% and 13%, preferably between 2% and 10%. If the mass fraction of this component is less than 0.5%, the glass melting temperature is high, the viscosity increases, the bubbles are not easy to be discharged, the glass is difficult to melt fully, and bubbles and stones are easy to appear. If the mass fraction of this component is higher than 13%, the elastic modulus and chemical stability of the glass deteriorate.

[0057] R is BaO, SrO, MgO, which belongs to alkaline earth metal oxides and is an intermediate of glass, and is used to improve the glass forming property of glass. The present invention controls the mass fraction of this component between 11% and 15%. If the mass fraction of this component is less than 11%, the improvement of the glass forming property of glass is not obvious; if the mass fraction of this component exceeds 15%, the chemical stability of glass is reduced.

[0058] M is Na2O and / or K2O. Na2O and K2O are the network outer oxides of the basic glass network, which can improve the chemical stability and surface tension of the glass, have the functions of high temperature fluxing, accelerating the melting of the glass, and reducing the high temperature viscosity of the glass, which is also beneficial to the clarification of the glass. The mass fraction of M is controlled between 1% and 5% in the present invention. If its content is lower than 1%, the expected effect cannot be achieved. If its content is higher than 5%, the glass will be easy to crystallize, and the thermal expansion coefficient of the glass will be too large, the chemical stability and mechanical properties of the glass will be reduced, and non-bridging oxygen will be generated to affect the permeability of the glass.

[0059] In some embodiments, in the aforementioned mid-infrared gallate glass, BaO: 5% to 7%.

[0060] BaO is a divalent network oxide that can increase the refractive index, density, gloss and chemical stability of glass. A small amount of BaO can accelerate the melting of glass, but too much BaO will cause secondary bubbles to appear during clarification. If the BaO content is less than 5%, its effect of accelerating glass melting is not obvious; when the BaO content is greater than 7%, it will increase the crystallization temperature of the glass, increase the crystallization tendency of the glass, and react with oxygen, making it difficult to clarify the melt.

[0061] In some embodiments, in the aforementioned mid-infrared gallate glass, except for BaO, the sum of the contents of other alkaline earth metal oxides and M is 9% to 11%; wherein the other alkaline earth metal oxides include SrO and / or MgO.

[0062] Specifically, within this range, the chemical properties of the glass are more stable, the mechanical properties are stronger, the transmittance is higher, and the glass is easier to melt.

[0063] In some embodiments, the aforementioned mid-infrared gallate glass further comprises TeO2, and the content of TeO2 is ≤12%.

[0064] Adding TeO2 can improve the chemical stability of glass, and make the glass have higher mechanical strength, better heat resistance and thermal shock resistance. At the same time, it can also improve the infrared transmittance of glass. However, if the TeO2 content is greater than 12%, it will affect the glass forming properties and cause crystallization.

[0065] In some embodiments, the aforementioned mid-infrared gallate glass further comprises Sb2O3 as a component.

[0066] The Sb2O3 component is used as a defoamer for glass. Preferably, the weight percentage of the component is controlled to be 0.02%-0.1%. If the weight percentage of the component is lower than 0.02%, it cannot be guaranteed that the bubbles in the glass are completely eliminated; if the weight percentage of the component exceeds 0.1%, the excess clarifier cannot react completely, reducing the homogenization effect of the glass.

[0067] The present invention provides a method for preparing any of the aforementioned mid-infrared gallate glasses, comprising the following steps:

[0068] After mixing the ingredients according to the formula, glass raw materials are obtained, the aforementioned glass raw materials are mixed evenly, melted at 1450-1500° C. for 6-12 hours, and cooled to obtain primary melting clinker;

[0069] The aforementioned primary melting clinker is melted in a vacuum environment at a melting temperature of 1450-1550° C. for a melting time of 4-8 hours, and then formed, annealed and cooled to obtain a mid-infrared gallate glass.

[0070] Specifically, the ingredients are prepared according to the following formula: in terms of oxide mass percentage, Ga2O3: 26% to 35%; Al2O3: 3.1% to 6.5%; CaO: 39% to 47%; Y2O3: 0.5% to 13%; R: 11% to 15%, wherein R is one or more of BaO, SrO, and MgO; and M: 1% to 5%, wherein M is Na2O and / or K2O.

[0071] After all the raw material components are evenly ground to form a mixture, they are placed in a crucible and placed in a silicon carbon rod electric furnace at 1450-1500°C for 4-8 hours, and naturally cooled to obtain a first-melting clinker. If the melting time is less than 4 hours, a homogeneous glass body cannot be obtained; if the melting time is more than 8 hours, energy is wasted.

[0072] The primary melting clinker is placed in a crucible and added to a vacuum melting furnace. The temperature is raised to 1450-1500°C for melting. The pressure in the furnace is evacuated to a vacuum degree of ≤3×10 -2 Pa; if the melting temperature is lower than 1450°C, the glass cannot be melted into a homogeneous glass body. If the melting temperature is higher than 1500°C, the equipment cannot withstand it. It is preferably 1450°C. In this way, the glass formed after melting is uniform, without obvious crystallization and stones, and will not cause significant damage to the crucible and equipment.

[0073] The glass liquid obtained by vacuum melting in the above steps is poured into a mold to form, and then annealed and cooled to obtain mid-infrared gallate glass.

[0074] In some embodiments, in the aforementioned preparation method, the vacuum degree of the aforementioned vacuum environment is ≤3×10 -2 Pa.

[0075] Specifically, if the vacuum degree is greater than 3×10 -2 Pa will cause a large amount of hydroxyl groups to exist in the glass, affecting the infrared transmittance of the glass.

[0076] The present invention provides a device comprising a window, wherein the window comprises any one of the aforementioned mid-infrared gallate glasses.

[0077] In some embodiments, the aforementioned device is an infrared detector, an infrared aircraft, a fairing or a hood.

[0078] The present invention will be further described below in conjunction with specific embodiments, but this should not be construed as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made to the present invention by technicians in this field based on the above-mentioned contents of the present invention still fall within the scope of protection of the present invention.

[0079] Unless otherwise specified, the materials, reagents, etc. involved below are all commercially available products well known to those skilled in the art; unless otherwise specified, the methods described are all methods well known in the art. Unless otherwise defined, the technical terms or scientific terms used should have the common meanings understood by ordinary technicians in the field to which the present invention belongs.

[0080] In the following embodiments, the infrared light transmittance spectrum is tested according to the test requirements, and the sample with a thickness of 2 mm after surface grinding and polishing is tested. The infrared band range of the test is 1μm~8μm infrared light transmittance; the glass transition temperature test adopts the German NETZSCH DSC analyzer, and the sample is ground and sieved and tested with powder, and the test temperature range is 100℃~1000℃; the moisture resistance of the sample is tested according to the inspection standard GB / T6582-1997; the acid resistance of the sample is tested according to the inspection standard GB / T6581-2007.

[0081] Example 1

[0082] This embodiment provides a mid-infrared gallate glass and a preparation method thereof.

[0083] According to the glass components and contents corresponding to the formula, the corresponding weight of raw materials is weighed, wherein CaO, BaO, Na2O and K2O are introduced in the form of corresponding carbonates. In terms of oxide mass percentage, the components of mid-infrared gallate glass include: Ga2O3: 26.19%; CaO: 41.46%; Al2O3: 4.57%; Y2O3: 11%; BaO: 7.28%; MgO: 6.61%; Na2O: 2.39%; K2O: 0.47%; and Sb2O3: 0.03%. After the raw materials are ground into powder and mixed evenly, they are melted at 1450°C for 12 hours and cooled to obtain a primary melting clinker.

[0084] The primary melting clinker is melted in a vacuum environment with a vacuum degree of 2×10 -2 Pa, the melting temperature is 1480℃, the melting time is 8h, and after complete melting, it is clarified, formed, annealed and cooled to obtain mid-infrared gallate glass.

[0085] The obtained mid-infrared gallate glass was tested. Its heat resistance was tested by differential scanning calorimetry. The differential scanning calorimetry curve is shown in Figure 1 As shown in Figure 1, its glass transition temperature is 714.4°C. The infrared transmittance of the mid-infrared gallate glass was tested, and its 0-8μm infrared light transmittance curve is shown in Figure 1. Figure 2 As shown, the infrared light transmittance curve from 900 to 1700 nm is as follows Figure 3As shown in the figure, the average transmittance of mid-infrared gallate glass under infrared light with a wavelength of 3.7 to 4.8 μm is 81.9%, and the average transmittance under infrared light with a wavelength of 900 to 1700 nm is 84.7%. The moisture resistance and acid resistance of mid-infrared gallate glass were tested, and its moisture resistance was grade A and its acid resistance was grade 3.

[0086] Example 2

[0087] This embodiment provides a mid-infrared gallate glass and a preparation method thereof.

[0088] The corresponding weight of raw materials is weighed according to the glass components and contents corresponding to the formula, wherein CaO, BaO, Na2O and K2O are introduced in the form of corresponding carbonates. In terms of oxide mass percentage, the components of mid-infrared gallate glass include: Ga2O3: 32.19%; CaO: 43.21%; Al2O3: 5.53%; Y2O3: 3.1%; BaO: 6.08%; MgO: 6.99%; Na2O: 1.36%; K2O: 0.51%; TeO2: 1%; and Sb2O3: 0.03%. The raw materials are ground into powder and mixed evenly, then melted at 1460°C for 12 hours and cooled to obtain a primary melting clinker.

[0089] The primary melting clinker is melted in a vacuum environment with a vacuum degree of 2.5×10 -2 Pa, the melting temperature is 1470℃, the melting time is 8h, and after complete melting, it is clarified, formed, annealed and cooled to obtain mid-infrared gallate glass.

[0090] The obtained mid-infrared gallate glass was tested. Its heat resistance was tested by differential scanning calorimetry. The differential scanning calorimetry curve is shown in Figure 4 As shown in Figure 1, its glass transition temperature is 708.4°C. The infrared transmittance of the mid-infrared gallate glass was tested, and its 0-8μm infrared light transmittance curve is shown in Figure 1. Figure 5 As shown, the infrared light transmittance curve from 900 to 1700 nm is as follows Figure 6 As shown in the figure, the average transmittance of mid-infrared gallate glass under infrared light with a wavelength of 3.7 to 4.8 μm is 82.4%, and the average transmittance under infrared light with a wavelength of 900 to 1700 nm is 84.8%. The moisture resistance and acid resistance of mid-infrared gallate glass were tested, and its moisture resistance was grade A and its acid resistance was grade 3.

[0091] As can be seen from Examples 1-2, the mid-infrared gallate glass provided by the present invention has high transmittance, with an average transmittance of more than 82% under infrared light with a wavelength of 3.7 to 4.8 μm, and an average transmittance of more than 84% under infrared light with a wavelength of 900 to 1700 nm. It is also resistant to high temperatures, has a moisture resistance of Class A, and has an acid resistance of Class 3, indicating that it has high chemical stability and strong adaptability to complex environments.

[0092] The technical features in the claims and / or the specification of the present invention may be combined, and the combination is not limited to the combination obtained by reference in the claims. The technical solution obtained by combining the technical features in the claims and / or the specification is also within the protection scope of the present invention.

[0093] The above description is only a preferred embodiment of the present invention and does not limit the present invention in any form. Any simple modification, equivalent change and modification made to the above embodiment according to the technical essence of the present invention still falls within the scope of the technical solution of the present invention.

Claims

1. A mid-infrared gallate glass, characterized in that: Measured in oxide mass percentage, its components include: Ga2O3: 26%~35%; CaO: 39%~47%; Al2O3: 3.1%~6.5%; Y2O3: 0.5%~13%; R: 11% to 15%, wherein R is one or more of BaO, SrO, and MgO; and M: 1% to 5%, M is Na2O and / or K2O.

2. The mid-infrared gallate glass according to claim 1, characterized in that: Ga2O3: 29% to 31%; and / or, CaO: 42% to 46%; and / or Al2O3: 3.5% to 6.0%; and / or, Y2O3:2%~10%.

3. The mid-infrared gallate glass according to claim 1, characterized in that: BaO: 5%~7%.

4. The mid-infrared gallate glass according to claim 3, characterized in that: Except for BaO, the sum of the contents of other alkaline earth metal oxides and M is 9% to 11%; Among them, other alkaline earth metal oxides include SrO and / or MgO.

5. The mid-infrared gallate glass according to claim 1, characterized in that: Its components also include TeO2, and the content of TeO2 is ≤12%.

6. The mid-infrared gallate glass according to claim 1, characterized in that: Its components also include Sb2O3.

7. A method for preparing the mid-infrared gallate glass according to any one of claims 1 to 6, characterized in that: The following steps are involved: After mixing the ingredients according to the formula, glass raw materials are obtained, the glass raw materials are mixed evenly, melted at 1450-1500° C. for 6-12 hours, and cooled to obtain a primary melting clinker; The primary melting clinker is melted in a vacuum environment at a melting temperature of 1450-1550° C. for a melting time of 4-8 hours, and then formed, annealed and cooled to obtain mid-infrared gallate glass.

8. The preparation method according to claim 7, characterized in that: The vacuum degree of the vacuum environment is ≤3×10 -2 Pa.

9. A device, characterized in that: It comprises a window, and the window comprises the mid-infrared gallate glass according to any one of claims 1 to 6.

10. The device according to claim 9, characterized in that The device is an infrared detector, an infrared aircraft, a fairing or a hood.

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